A promising approach in the selective separation and modification of cellulose from raw biomass under a mild alkali process was proposed. In our study, ball milling was applied to wheat straw prior to alkali treatment. With ball milling, ultrafine powder formed an amorphous microstructure and displayed a level of solubilization in aqueous NaOH higher than that of general ground samples. Alkali-treated ultrafine powder resulted in up to 93.76% removal of hemicellulose and 86.14% removal of lignin, whereas cellulose remains largely undissolved. A high glucose yield (98.48%) was obtained via a 72 h enzymatic hydrolysis. X-ray diffraction and solid state ¹³C cross-polarization magic angle spinning nuclear magnetic resonance analysis revealed evidence of the transformation of crystalline cellulose I to cellulose II in alkali-treated ultrafine wheat straw. Prolonging the alkaline treatment time can significantly decrease the level of cellulose hydrogen bonding and increase the hydrolysis yield. The combination of ultrafine ball milling and low-severity alkali treatment played a significant role in the cellulose supramolecular change, which can then be used for downstream biorefinery processes or as a feedstock for the biomaterial industry.

Background: High-solids enzymatic hydrolysis has attracted increasing attentions for the production of bioethanol from lignocellulosic biomass with its advantages of high product concentration, water saving, and low energy and capital costs. However, the increase of solids content would worsen the rheological properties, resulting in heat/mass transfer limitation and higher mixing energy. To address these issues, ball milling was applied to corn stover prior to enzymatic hydrolysis, and the rheological behaviors and digestibility of ball-milled corn stover under high-solids loading were investigated.Results: Ball milling significantly modified the physicochemical properties of corn stover. The apparent viscosity of slurries at 30% solid loading decreased by a factor of 500 after milling for 60 min, and the yield stress was less than 10 Pa. The dramatic decrease of viscosity and yield stress enabled the hydrolysis process to be conducted in shake flask, and remained good mixing. Meanwhile, the estimated energy consumption for mixing during saccharification decreased by 400-fold compared to the untreated one. The resultant hydrolysate using 10 FPU g⁻¹solids was determined to contain 130.5 g L⁻¹fermentable sugar, and no fermentation inhibitors were detected.Conclusions: The proposed ball milling pretreatment improved rheological behavior and sugar yield of high-solids corn stover slurry. Ball milling enables high-solids slurry to maintain low viscosity and yield stress while obtaining a non-toxic high-concentration fermentable syrup, which is undoubtedly of great significance for inter-unit processing, mixing and downstream process. In addition, the energy input for ball milling could be balanced by the reduced mixing energy. Our study indicates ball milling a promising pretreatment process for industrial bioethanol production.